EP1644440B1 - Rubber-reinforced vinyl aromatic polymers - Google Patents

Rubber-reinforced vinyl aromatic polymers Download PDF

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Publication number
EP1644440B1
EP1644440B1 EP04740634.3A EP04740634A EP1644440B1 EP 1644440 B1 EP1644440 B1 EP 1644440B1 EP 04740634 A EP04740634 A EP 04740634A EP 1644440 B1 EP1644440 B1 EP 1644440B1
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Prior art keywords
weight
particles
rubber
vinyl aromatic
morphology
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EP04740634.3A
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German (de)
English (en)
French (fr)
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EP1644440A1 (en
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Alessandro Casalini
Luca Monti
Anna Grazia Rossi
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Versalis SpA
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Versalis SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to a process for rubber-reinforced vinyl aromatic polymers.
  • compositions comprising a rigid matrix consisting of vinyl aromatic polymers or copolymers and a rubbery phase dispersed inside the matrix in the form of particles with a strictly bimodal distribution or morphology.
  • HIPS high impact polystyrene
  • the patent US 4,153,645 describes a HIPS with an enhanced property balance obtained by mechanically mixing (melt-blending) 50-85% by weight of a high impact polystyrene containing small rubbery particles (with an average diameter of about 0.2-0.9 ⁇ m) with 15-50% by weight of a high impact polystyrene containing larger rubbery particles (average diameter of about 2-5 ⁇ m).
  • the final product obtained by mixing the two HIPS has impact and flexural resistance values higher than those expected by applying the blend rule, without any decrease in the other physical properties.
  • US patent 4,493,922 describes a HIPS with a bimodal morphology consisting of 60-95% by weight of "capsule” particles having a diameter of between 0.2 and 0.6 ⁇ m and 40-5% by weight of particles with a "cell” and/or “coil” morphology, with a diameter ranging from 2 to 8 ⁇ m.
  • a second styrene dissolution of a high viscosity polybutadiene rubber is feed in the remaining third of the reactor.
  • the high viscosity polybutadiene when in contact with the previously formed pre-polymer, undergoes a rapid phase inversion, forming large particles, poorly grafted and which cannot be easily modulated as far as the dimension is concerned.
  • US 5,240,993 describes a method ("parallel polymerization") for the preparation of impact resistance vinyl aromatic polymers, characterized by a bimodal distribution of the rubbery phase, according to a continuous mass process, using two plug flow reactors situated in parallel.
  • a first pre-polymer containing a rubbery phase with small particles is prepared in one of the two reactors, whereas a second pre-polymer, containing a rubbery phase with large particles, is prepared in the other reactor.
  • the polymeric streams are mixed at the outlet of the two reactors and the polymerization is completed in a third reactor, again of the plug flow type, called finishing reactor.
  • WO97/39040 describes a simplified version of this process, according to which, large particles are produced in the first half of a pre-polymerization reactor by feeding a suitable styrene solution of a high viscosity rubber, under such conditions as to guarantee a good grafting efficiency and an accurate dimensional control.
  • the large-particle pre-polymer is mixed in the second half of the same reactor, in suitable proportions, with a second pre-polymer having small particles, previously produced in a reactor placed in series with the first.
  • European patent 418,042 describes a method for producing rubber-reinforced vinyl aromatic polymers, in which the particles have a "generally bimodal" distribution or a broader distribution including, in addition to the small (0.1-0.8 ⁇ m) prevalent modal class and the large (2-6 ⁇ m) subvalent modal class, also a third particle class having an intermediate dimension (0.8-2.0 ⁇ m). This distribution is obtained with a medium cis polybutadiene characterized by a bimodal distribution of the molecular weights and sold under the name of ASAPRENE 760 A.
  • European patent 731,016 similarly, describes the production of HIPS with a bimodal morphology using, in a conventional configuration of reactors, an elastomeric phase (dissolved in styrene) consisting of a medium cis and low viscosity polybutadiene and a high cis and high viscosity polybutadiene.
  • European patent 726,280 describes the production of HIPS with a bimodal morphology by introducing suitable concentrations of stable nitroxyl radicals during the HIPS polymerization step, with a conventional reactor configuration and with a high cis polybutadiene rubber.
  • European patent 620,236 proposes a method for obtaining HIPS with a "strictly bimodal" morphology. According to this method, a small amount of HIPS with large particles is dissolved in styrene together with the polybutadiene rubber or styrene-butadiene block copolymer necessary for producing the prevalent modal class of small particles.
  • the solution obtained is polymerized with a conventional plant configuration. During the whole polymerization the cross-linked rubbery particles of the preformed HIPS do not undergo retro-inversion but keep their structure and dimension, whereas the polybutadiene rubber or styrene-butadiene copolymer form small particles with a corresponding structure and dimensions.
  • the basic limit of the technical solution proposed in this patent is represented by the highest percentage of preformed HIPS which can be dissolved in styrene together with the rubber (lower than 5%).
  • the Applicant has now found new rubber-reinforced vinyl aromatic polymers, having a strictly bimodal distribution of the rubbery particles, which do not have the typical drawbacks of the products of the known art, which can be obtained with standard production configurations and which have excellent physico-mechanical properties, mainly in terms of gloss and impact resistance.
  • the present invention uses rubber-reinforced vinyl aromatic (co)polymers, having a strictly bimodal morphology, which consist of from 55 to 90% by weight of rigid polymeric matrix and from 10 to 45% by weight of a rubbery phase dispersed inside said rigid polymeric matrix in the form of grafted and occluded particles and wherein said rubber particles consist of from 60 to 99% by weight, preferably 70-95%, of particles with a capsule or "core-shell" morphology and from 1 to 40% by weight, preferably 5-30%, of particles with a "salami” morphology, said percentages being measured on the basis of the weight of the rubber particles only.
  • rubber-reinforced vinyl aromatic (co)polymers having a strictly bimodal morphology, which consist of from 55 to 90% by weight of rigid polymeric matrix and from 10 to 45% by weight of a rubbery phase dispersed inside said rigid polymeric matrix in the form of grafted and occluded particles and wherein said rubber particles consist of from 60 to 99% by weight,
  • vinyl aromatic (co)polymer essentially refers to a product obtained from the polymerization of at least one monomer having the following general formula: wherein R is a hydrogen or a methyl group, n is zero or an integer ranging from 1 and 5 and Y is a halogen such as chlorine or bromine, or an alkyl or alkoxyl radical having from 1 to 4 carbon atoms.
  • vinyl aromatic monomers having the above general formula are: styrene, ⁇ -methyl styrene, methyl styrene, ethyl styrene, butyl styrene, dimethyl styrene, mono-, di-, tri-, tetra- and penta-chloro styrene, bromo styrene, methoxy styrene, acetoxy styrene, etc..
  • Styrene and ⁇ -methyl styrene are preferred vinyl aromatic monomers.
  • the vinyl aromatic monomers having general formula (I) can be used alone or blended with other monomers which can co-polymerize.
  • the amount of copolymerizable monomer can be up to 40% by weight, generally from 15 to 35%, with respect to the total mixture of monomers.
  • Examples of said monomers are (meth)acrylic acid, C 1 -C 4 alkyl esters of (meth) acrylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, butyl acrylate, amides and nitriles of (meth)acrylic acid such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, butadiene, ethylene, divinyl benzene, maleic anhydride, etc.
  • Preferred monomers which can co-polymerize are acrylonitrile and methyl methacrylate.
  • the core-shell particles have an average diameter of between 0.10 and 0.30 ⁇ m, preferably between 0.15 and 0.25 ⁇ m, whereas the particles with a "salami" structure have an average diameter of between 1 and 5 ⁇ m, preferably between 2 and 4 ⁇ m.
  • Elastomeric products capable of supplying a rubbery phase dispersed in the rigid polymeric matrix in the form of grafted and occluded particles with a capsule or "core-shell" morphology, are selected from homopolymers and copolymers of 1,3-alkadienes containing 40-100% by weight of 1,3-alkadiene monomer, for example 1,3-butadiene, and 0-60% by weight of one or more mono-ethylenically unsaturated monomers selected from styrene, acrylonitrile, ⁇ -methyl styrene, methyl methacrylate, ethyl acrylate.
  • 1,3-alkadienes copolymers are styrene-butadiene block copolymers, such as linear di-block rubbers of the S-B type, wherein S represents a polystyrene block having an average molecular weight Mw between 5,000 and 80,000, whereas B represents a polybutadiene block with an average molecular weight Mw between 2,000 and 250,000.
  • S represents a polystyrene block having an average molecular weight Mw between 5,000 and 80,000
  • B represents a polybutadiene block with an average molecular weight Mw between 2,000 and 250,000.
  • the amount of S block ranges from 10 to 50% by weight with respect to the total S-B rubber.
  • the preferred product is a styrene-butadiene block copolymer having a styrene content equal to 40% by weight and viscosity in solution, measured at 23°C in a solution of 5% styrene by weight, ranging from 35 to 50 cPs.
  • Elastomeric products capable of providing a rubbery phase dispersed in the rigid polymeric matrix in the form of grafted and occluded particles with a "salami” morphology are selected from homopolymers and copolymers of olefins or 1,3 alkadienes incompatible with the elastomeric products which produce the capsule rubbery phase.
  • the criterion for choosing said incompatible elastomers is that the difference between the solubility parameter ( ⁇ ), according to Hildebrand, of the elastomer which produces the "capsule” rubbery particles and the solubility parameter, again according to Hildebrand, of the elastomer which produces the "salami” rubbery particles, is higher than or equal to 0.5.
  • Information on the solubility parameter can be found in " CRC Handbook of Polymer-Liquid Interaction Parameters and Solubility Parameters" - Allan F.M. Barton - CRC Press Boca Raton, Bost on.
  • the preferred product is polyisoprene with a solution viscosity, measured as per above, of between 100 and 1000 cPs.
  • the object of the present invention relates to a continuous-mass process for the preparation of rubber-reinforced vinyl aromatic (co)polymers, with a strictly bimodal morphology, consisting of from 55 to 90% by weight of rigid polymeric matrix and from 10 to 45% by weight of a dispersed rubbery phase inside said rigid polymeric matrix, in the form of grafted and occluded particles, wherein said rubber particles consist of from 60 to 99% by weight of particles with a "capsule” or “core-shell” morphology and from 1 to 40% by weight, preferably 5-30%, of particles with a "salami” morphology, said process comprising:
  • the process object of the present invention can be carried out in continuous using the equipment normally used for preparing traditional reinforced vinyl aromatic (co)polymers, such as PFR plug flow reactors or CFSTR reactors whose operating conditions are described, for example, in USA patents 2,727,884 or 3,903,202 .
  • the rubbers are dissolved in the monomers possibly in the presence of an inert solvent in quantities ranging from 5 to 20% by weight with respect to the total.
  • inert solvents which can be used in the process object of the present invention include aromatic hydrocarbons which are liquid at the polymerization temperature, such as, for example, toluene, ethyl benzene, xylenes, or mixtures thereof.
  • the dissolution of the rubbers in the mixture of monomers and possible solvent is carried out in a mixer maintained at a temperature not higher than 100°C.
  • the reactors are maintained, during the polymerization reaction, at a pressure higher than the pressure at which the components fed evaporate.
  • the pressure normally ranges from 0.5 to 5 bar whereas the temperature preferably ranges from 70 to 150°C.
  • the temperature is distributed in order to have two or more zones heated at different temperatures.
  • the initiators used are of the conventional type adopted for the polymerization of styrene, such as, for example, organic peroxy radicalic initiators.
  • organic peroxy radicalic initiators examples include: dibenzoyl peroxide, tert-butyl peroctoate, tert-butyl perbenzoate, di-tert-butyl peroxide, 1,1'-di-tert-butyl peroxy-3,3,5-trimethyl cyclohexane, 1,1'-di-tert-butyl peroxy cyclohexane, etc..
  • These initiators are added in quantities ranging from 0.005 to 0.5% by weight with respect to the monomer.
  • the chain transfer agents are also those conventionally used in styrene polymerization and are selected from mercaptans such as, for example, n-dodecyl mercaptan, t-dodecyl mercaptan (TDM), lauryl mercaptan, stearyl mercaptan, benzyl mercaptan cyclohexyl mercaptan, etc.. These chain transfer agents are added in quantities ranging from 0.005 to 0.5% by weight with respect to the monomer.
  • mercaptans such as, for example, n-dodecyl mercaptan, t-dodecyl mercaptan (TDM), lauryl mercaptan, stearyl mercaptan, benzyl mercaptan cyclohexyl mercaptan, etc.
  • the possible solvents present and the non-reacted monomers are removed under vacuum and at a high temperature (200-260°C), whereas the resulting polymer is extruded, cooled and cut into pellets of the desired dimensions.
  • the gaseous products which have been removed are condensed and possibly recycled.
  • the process, object of the present invention can be carried out in a completely equivalent manner, by means of a batch process in mass-suspension, using stirred autoclaves of the batch-reactor type.
  • a second further object of the present invention therefore relates to a mass-suspension process for the preparation of rubber-reinforced vinyl aromatic (co)polymers having strictly bimodal morphology, consisting of from 55 to 90% by weight of a rigid polymeric matrix and from 10 to 45% by weight of a rubbery phase dispersed inside said rigid polymeric matrix in the form of grafted and occluded particles, and wherein said rubber particles consist of 60 to 99% by weight of particles with a capsule or "core-shell" morphology and from 1 to 40% by weight, preferably 5-30%, of particles with a "salami" morphology, said process including:
  • the rubbers selected from those previously indicated are dissolved in the monomers possibly in the presence of an inert solvent, in quantities ranging from 5 to 20% by weight with respect to the total.
  • inert solvents which can be used in the process object of the present invention are aromatic hydrocarbons which are liquid at the polymerization temperature, such as, for example, toluene, ethyl benzene, xylenes, or mixtures thereof.
  • the dissolution of the rubbers in the monomer mixture and possible solvent is carried out in the same pre-polymerization autoclave (batch reactor) maintained at a temperature not higher than 100°C.
  • the reactor is maintained at a pressure higher than that at which the components fed evaporate. Normally the pressure ranges from 0.5 to 5 bar, whereas the temperature is preferably between 70 and 150°C, with a stirring rate of between 10 and 100 rpm.
  • the initiators used are those conventionally adopted in the polymerization styrene of styrene such as, for example, the organic peroxide radicalic initiators previously cited.
  • Examples of these initiators are: dibenzoyl peroxide, tert-butyl peroctoate, tert-butyl perbenzoate, di-tert-butyl peroxide, 1,1'-di-tert-butyl peroxy-3,3,5-trimethyl cyclohexane, 1,1'-di-tert-butyl-peroxy cyclohexane, etc.. These initiators are added in amounts ranging from 0.005 to 0.5% by weight with respect to the monomer.
  • the chain transfer agents are also those conventionally used in the polymerization of styrene, cited above.
  • Examples of chain transfer agents are selected from mercaptans such as, for example, n-dodecyl mercaptan, t-dodecyl mercaptan (TDM), lauryl mercaptan, stearyl mercaptan, benzyl mercaptan, cyclohexyl mercaptan, etc..
  • TDM n-dodecyl mercaptan
  • TDM t-dodecyl mercaptan
  • lauryl mercaptan lauryl mercaptan
  • stearyl mercaptan stearyl mercaptan
  • benzyl mercaptan cyclohexyl mercaptan
  • the polymer is transferred to a second autoclave of the batch type, it is suspended in an aqueous phase (water/organic phase weight ratio of between 1/1 and 3/2), containing one or more suspending agents, for example sodium chloride, sodium naphthalene sulfonate and/or poly-[(acrylic acid)-co-(2-ethyl-hexyl-acrylate)], possible peroxy initiators or mercaptan chain transfer agents are added and the polymerization is completed, by heating to temperatures of between 100 and 170°C, until a full conversion of monomers to polymer is reached. At the end, the polymer is recovered with traditional methods.
  • suspending agents for example sodium chloride, sodium naphthalene sulfonate and/or poly-[(acrylic acid)-co-(2-ethyl-hexyl-acrylate)]
  • possible peroxy initiators or mercaptan chain transfer agents are added and the polymerization is completed, by heating to temperatures of between 100 and 1
  • 30 g of di-tert-butyl peroxide are added and the polymerization is carried out until the total conversion of the monomer and cross-linking of the rubbery phase, by heating under stirring for 1 hour at 120°C, 2 hours at 140°C and 3 hours at 155°C.
  • Example 1 is repeated with the only difference that instead of the BUNA BL 6533 TC copolymer alone, a blend is used consisting of 3.6 kg of BUNA BL 6533 TC copolymer and of 0.6 kg of polyisoprene IR 2200 L (NIPPON ZEON).
  • Example 2 is repeated, with the only difference that a blend consisting of 3.0 kg of BUNA BL 6533 TC copolymer and of 1.2 kg of polyisoprene IR 2200 L (NIPPON ZEON) is used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
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EP04740634.3A 2003-07-11 2004-07-02 Rubber-reinforced vinyl aromatic polymers Active EP1644440B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04740634T PL1644440T3 (pl) 2003-07-11 2004-07-02 Wzmacniane kauczukiem aromatyczne polimery winylowe

Applications Claiming Priority (2)

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IT001420A ITMI20031420A1 (it) 2003-07-11 2003-07-11 Polimeri vinilaromatici rinforzati con gomma
PCT/EP2004/007296 WO2005005539A1 (en) 2003-07-11 2004-07-02 Rubber-reinforced vinyl aromatic polymers

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EP1644440B1 true EP1644440B1 (en) 2020-01-15

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US (2) US7906576B2 (ru)
EP (1) EP1644440B1 (ru)
JP (2) JP5202843B2 (ru)
CN (1) CN100482735C (ru)
BR (1) BRPI0411719A (ru)
CA (1) CA2531748C (ru)
ES (1) ES2784012T3 (ru)
HU (1) HUE048778T2 (ru)
IT (1) ITMI20031420A1 (ru)
MX (1) MXPA06000461A (ru)
PL (1) PL1644440T3 (ru)
RU (1) RU2346964C2 (ru)
SA (1) SA04250208B1 (ru)
WO (1) WO2005005539A1 (ru)

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US7906576B2 (en) 2011-03-15
WO2005005539A1 (en) 2005-01-20
EP1644440A1 (en) 2006-04-12
US20110124813A1 (en) 2011-05-26
US20070149686A1 (en) 2007-06-28
JP5202843B2 (ja) 2013-06-05
MXPA06000461A (es) 2006-04-11
SA04250208B1 (ar) 2008-03-26
BRPI0411719A (pt) 2006-08-08
JP2011241407A (ja) 2011-12-01
CN100482735C (zh) 2009-04-29
CN1820049A (zh) 2006-08-16
RU2346964C2 (ru) 2009-02-20
JP2009513746A (ja) 2009-04-02
CA2531748A1 (en) 2005-01-20
CA2531748C (en) 2014-10-07
PL1644440T3 (pl) 2020-06-29
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HUE048778T2 (hu) 2020-08-28
ITMI20031420A1 (it) 2005-01-12

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